EP1094031A1 - Zylindrischer einrohr-reformer und verfahren zu dessen verwendung - Google Patents

Zylindrischer einrohr-reformer und verfahren zu dessen verwendung Download PDF

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EP1094031A1
EP1094031A1 EP00917380A EP00917380A EP1094031A1 EP 1094031 A1 EP1094031 A1 EP 1094031A1 EP 00917380 A EP00917380 A EP 00917380A EP 00917380 A EP00917380 A EP 00917380A EP 1094031 A1 EP1094031 A1 EP 1094031A1
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Prior art keywords
cylinder
catalyst layer
layer
reformer
radial direction
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EP00917380A
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English (en)
French (fr)
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EP1094031A4 (de
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Toshiyasu Tokyo Gas Co. Ltd. Miura
Yoshinori Tokyo Gas Co. Ltd. Shirasaki
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Tokyo Gas Co Ltd
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Tokyo Gas Co Ltd
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Publication of EP1094031A1 publication Critical patent/EP1094031A1/de
Publication of EP1094031A4 publication Critical patent/EP1094031A4/de
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    • H01M8/0612—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants from carbon-containing material
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Definitions

  • the present invention relates to a single-pipe cylinder type reformer for manufacturing a hydrogen-rich reformed gas by steam-reforming a hydrocarbon-based crude fuel such as town gas, natural gas, or LPG or an alcohol and, more particularly, to a reformer used in combination with a polymer electrolyte fuel cell.
  • a reformer is an apparatus for producing a (hydrogen-rich) reformed gas having a high hydrogen concentration by steam-reforming a hydrocarbon-based crude fuel such as town gas, natural gas, and/or LPG or an alcohol.
  • This apparatus is widely used to produce hydrogen used in the process of manufacturing optical fibers or semiconductors and for fuel cells and the like.
  • the reforming reaction in the reformer is expressed as: CH 4 + H 2 O ⁇ CO + 3H 2 (CH 4 + H 2 O ⁇ CO + 3H 2 ) CO + H 2 O ⁇ CO 2 + H 2 (CO + H 2 O ⁇ CO 2 + H 2 )
  • the steam reforming reaction caused by the reformer is an endothermic reaction, and hence heating is required to sustain the reaction.
  • a combustion unit such as a burner is provided for the reformer, and heating is performed by burning surplus hydrogen from a reformation material gas or fuel cell.
  • a single-pipe cylinder type reformer like the one disclosed in Japanese Unexamined Patent Publication No. No. 11-11901 is known.
  • This single-pipe cylinder type reformer is configured to have a heating means such as a burner in a cylindrical vessel incorporating a catalyst layer between two cylinders so as to heat the catalyst layer with the heating means and steam-reform a reformation material gas passed through the catalyst layer.
  • a heating means such as a burner in a cylindrical vessel incorporating a catalyst layer between two cylinders so as to heat the catalyst layer with the heating means and steam-reform a reformation material gas passed through the catalyst layer.
  • Fig. 1 is a longitudinal sectional view showing the schematic arrangement of a conventional single-pipe cylinder type reformer.
  • an upright elongated outer cylinder 1 having a circular cross-section, a circular inner cylinder 3 located inside the outer cylinder 1, an intermediate cylinder 2 located inside the outer cylinder 1 to surround the inner cylinder 3 at a predetermined distance therefrom, and a radiation cylinder 4 located inside the inner cylinder 3 are concentrically disposed, and the annular space between the inner cylinder 3 and the intermediate cylinder 2 is filled with a reforming catalyst 5.
  • a burner 7 supported on a burner mount base 6 is disposed in the upper portion of a combustion chamber 9 located inside the radiation cylinder 4.
  • a cover plate (bottom plate) 1a which is a common one-piece plate is attached to the lower ends of the outer cylinder 1 and inner cylinder 3.
  • the burner 7 is disposed in the upper portion of the combustion chamber 9. However, the burner 7 is disposed in the lower portion of the combustion chamber 9 in some case (not shown).
  • the cover plate 1a is attached as a ceiling plate, which is a common one-piece disk, attached to the upper ends of the outer cylinder 1 and inner cylinder 3.
  • the single-pipe cylinder type reformer shown in Fig. 1 operates as follows.
  • the burner 7 generates a high-temperature combustion gas in the combustion chamber 9 with a combustion flame 8.
  • the heat is transferred outside the inner cylinder in the radial direction via the radiation cylinder 4 to heat the reforming catalyst 5.
  • the high-temperature combustion gas enters the inner cylinder 3 from the lower portion of the radiation cylinder 4 to become an ascending current, thereby directly heating the reforming catalyst 5.
  • the combustion gas is discharged from the upper end portion of the reformer after heating.
  • the reformation material gas which is fed from the upper portion of the reformer is heated to about 700°C while descending the annular flow path filled with the reforming catalyst 5. As a consequence, steam reforming is sufficiently performed.
  • the reformed material gas (reformed gas) is reversed in the lower end portion of the reformer to become an ascending current in the path formed between the outer cylinder 1 and the inner cylinder 3. Meanwhile, the sensible heat of the reformed gas is recovered in the reforming step inside the intermediate cylinder 2. As a result, the temperature of the reformed gas lowers, and the gas is extracted outside as a reformed gas from the upper end portion of the reformer.
  • the conventional single-pipe cylinder type reformer shown in Fig. 1 suffers the following problems.
  • the required improvements include a reduction in fuel by efficient preheating of a reformation material gas, an improvement in operability by prevention of overheating of a steam generator, an increase in efficiency by the preservation of a necessary temperature inside the reformer and the effective use of heat quantity, suppression of heat radiation to the outside by an effective heat insulating structure, realization of high durability by a reduction in heat stress due to an inner temperature difference, an increase in efficiency of steam generation by the effective use of reaction heat, and an operation method capable of efficiently coping with variations in operation state.
  • the reformed gas produced by the conventional single-pipe cylinder type reformer contains about 10% of CO.
  • the CO concentration must be decreased to about 0.5% by using a CO transformer, and a CO selective oxidation reaction must be caused by using a CO selective oxidizing unit to decrease the CO concentration to about 10 ppm.
  • separately providing the CO transformer and CO selective oxidizing unit for the single-pipe cylinder type reformer is not preferable in terms of a reduction in size, an increase in efficiency, and starting characteristics.
  • the present invention has been made in consideration of the above problems in the prior art, and has as its first object to provide a single-pipe cylinder type reformer which prevents the generation of thermal stresses by liberating thermal displacement of outer and inner cylinders forming a reformer in the axial direction, prevents the occurrence of buckling of the inner cylinder and a deterioration in the performance of the reformer due to the buckling, in particular, and reduces a heat radiation loss from a combustion chamber through a cover plate.
  • a single-pipe cylinder type reformer characterized by comprising an upright outer circular cylinder, a circular cylinder concentrically located inside the outer cylinder at a distance in a radial direction, a circular intermediate cylinder unit concentrically located between the outer cylinder and the inner cylinder at a distance in the radial direction, a circular radiation cylinder concentrically located inside the inner cylinder at a distance in the radial direction, a burner fixed to one end portion of the reformer in an axial direction to be located in the center of the radiation cylinder in the radial direction, and a plurality of annular flow paths formed in laminar shapes in the radial direction between the inner cylinder and the intermediate cylinder unit and between the intermediate cylinder unit and the outer cylinder, the annular flow paths being at least partly filled with a reforming catalyst serving as a reforming catalyst layer and communicating with each other, wherein end portions of the outer and inner cylinders in
  • the burner is fixed to an upper end of the reformer, and the cover plates are respectively mounted on lower ends of the outer and inner cylinders.
  • the burner is fixed to a lower end of the reformer, and the cover plates are respectively mounted on upper ends of the outer and inner cylinders.
  • a steam generator is further disposed inside or outside the reformer.
  • the single-pipe cylinder type reformer according to the first aspect of the present invention is used for a fuel cell.
  • a single-pipe cylinder type reformer comprising an upright outer circular cylinder, a circular cylinder concentrically located inside the outer cylinder at a distance in a radial direction, a plurality of circular intermediate cylinders concentrically located between the outer cylinder and the inner cylinder at distances from each other in the radial direction, a circular radiation cylinder concentrically located inside the inner cylinder at a distance in the radial direction, a burner fixed to one end portion of the reformer in an axial direction to be located in the center of the radiation cylinder in the radial direction, and a plurality of annular flow paths formed in laminar shapes in the radial direction between the inner cylinder and the innermost intermediate cylinder, between the adjacent intermediate cylinders, and between the outermost intermediate cylinder and the outer cylinder, the annular flow paths being at least partly filled with a reforming catalyst serving as a reforming catalyst layer and communicating with each other, the present invention has the following characteristic aspects.
  • Fig. 2 is a longitudinal sectional view showing the schematic arrangement of a single-pipe cylinder type reformer according to the first embodiment of the present invention.
  • an elongated outer cylinder 1 having a circular cross-section is disposed upright, and an elongated inner cylinder 3 having a circular cross-section is concentrically located inside the outer cylinder 1.
  • An intermediate cylinder 2 surrounding the inner cylinder 3 is located inside the outer cylinder 1 at a predetermined distance from the inner cylinder 3.
  • the annular space defined between the inner cylinder 3 and the intermediate cylinder 2 is filled with a reforming catalyst 5.
  • a radiation cylinder 4 is also concentrically located inside the inner cylinder 3.
  • a burner 7 is mounted in the upper portion of a combustion chamber 9 formed inside the radiation cylinder 4 via a burner mount base 6.
  • cover plates (bottom plates) 1b and 3a are hermetically fixed to the lower end portions of the outer cylinder 1 and inner cylinder 3 in the axial direction, respectively, which oppose the burner 7, by welding or the like.
  • a predetermined space is defined between the cover plate 1b of the outer cylinder 1 and the cover plate 3a of the inner cylinder 3.
  • the cover plates 1b and 3a form a double structure with respect to the center direction of the outer cylinder 1 and inner cylinder 3.
  • the burner 7 and burner mount base 6 are disposed on the upper portion of the combustion chamber 9, and the cover plates (bottom plates) 1b and 3a are respectively attached to the lower ends of the outer cylinder 1 and inner cylinder 3 to form a double structure.
  • the burner 7 and burner mount base 6 may be disposed on the lower portion of the combustion chamber 9.
  • the cover plates (ceiling plates in this case) of the inner cylinder 3 and outer cylinder 1 form a double structure (not a common one-piece disk). The distance between the cover plates 1b and 3a in the axial direction is properly determined in consideration of the thermal displacement difference between the outer cylinder 1 and the inner cylinder 3 in the axial direction and prevention of natural convection of a reformed gas.
  • a steam generator for generating/supplying steam to be fed into the reformer together with a reformation material gas such as a town gas is provided inside or outside the reformer.
  • the reformer shown in Fig. 2 operates as follows.
  • a fuel formed by a town gas (13A) and combustion air are supplied to the burner 7 and burnt, they burst into a combustion flame 8 in the combustion chamber 9.
  • the combustion chamber 9 is then filled with a high-temperature combustion gas.
  • the heat of this high-temperature combustion gas indirectly heats the reforming catalyst 5 via the radiation cylinder 4.
  • the gas enters the inner cylinder 3 from the lower portion of the radiation cylinder 4 to become an ascending current, and directly heats the reforming catalyst 5 via the wall of the inner cylinder 3.
  • the gas is then discharged from the upper end portion of the reformer.
  • the reformation material gas made up of the town gas fed from the upper portion of the reformer and the steam supplied from the steam generator (not shown) is heated to about 700°C by the combustion gas while descending the annular flow path filled with the reforming catalyst.
  • steam reforming is sufficiently done.
  • the temperature of the reforming catalyst becomes highest at the lower end portion of the annular flow path filled with the reforming catalyst, i.e., near the lower end of the intermediate cylinder 2.
  • the reformed gas flowing out from the lower end portion of the annular flow path reverses and becomes an ascending current. While the reformed gas ascends, its latent heat is recovered in the reforming step inside the intermediate cylinder 2.
  • the temperature of the gas lowers, and the gas is extracted as a hydrogen-rich reformed gas (a gas mixture of hydrogen, CO, CO 2 , and the like) from the upper end portion of the reformer.
  • the present invention provides a single-pipe cylinder type reformer which produces a gas with a low CO concentration, operates efficiently, has good starting characteristics, realizes reductions in size and weight, and is thermally stable and efficient.
  • Fig. 3 shows an example of the schematic arrangement of a compact, lightweight, single-pipe cylinder type reformer.
  • a reformer 81 is comprised of an outer cylinder 10, an intermediate cylinder group 60 concentrically located in the outer cylinder 10, an inner cylinder 68 concentrically located inside these intermediate cylinders, a reforming catalyst layer 13 disposed in the annular space defined between the inner cylinder 68 and an innermost intermediate cylinder 67, a CO converter catalyst layer 11 (to be also referred to as a shift layer 11 hereinafter) disposed in the annular space defined between intermediate cylinders 65 and 64, a CO selective oxidizing catalyst layer 12 (to be also referred to as a PROX layer 12 hereinafter) disposed in the annular space defined between an outermost intermediate cylinder 61 and a second outermost intermediate cylinder 62, and the like.
  • a heat transfer partition wall 14 (radiation cylinder) is concentrically located inside the inner cylinder 68.
  • a burner 18 is mounted inside the heat transfer partition wall 14 via a burner mount base 16.
  • the outer cylinder 10 is a closed-end cylinder having a circular cross-section.
  • the side surface of the upper portion of the outer cylinder 10 has a saturated or superheated steam outlet 20, wet steam outlet 21, water supply port 22, combustion exhaust gas outlet 24, supply port 26 for a fluid mixture of a reformation material gas and steam, reformed gas outlet 28, and supply port 30 for PROX layer air.
  • the intermediate cylinder group 60 is constituted by the first to seventh intermediate cylinders 61 to 67, and annular spaces are defined between the respective intermediate cylinders.
  • An air path 42 for supplying air to the PROX layer 12 is formed between the first intermediate cylinder 61 and the outer cylinder 10. This air path 42 communicates throughout the circumference at the bottom to form a jacket structure surrounding the overall apparatus with an air layer.
  • the first intermediate cylinder 61 also has air inlets 43 for feeding air, which are formed in a bottom 71 and the side surface.
  • the upper and lower PROX layers 12 are formed between the first and second intermediate cylinders 61 and 62.
  • Each PROX layer 12 is made up of a PROX catalyst layer 44 and air mixing layer 46.
  • a lower PROX layer 12a communicates with the shift layer 11, located inward therefrom, at the lower portion.
  • a lower PROX layer 12b is connected to the reformed gas outlet 28 at the upper portion.
  • the reformed gas outlet 28 is connected to, for example, a fuel gas supply pipe 102 of a polymer electrolyte fuel cell 100.
  • a reformed gas d (fuel gas) which contains hydrogen having a predetermined concentration and is extracted from the reformed gas outlet 28 is supplied to the fuel electrode side (not shown) of the polymer electrolyte fuel cell 100. With this operation, electric power generation is performed.
  • a surplus reformed gas e in the polymer electrolyte fuel cell 100 may be used as a combustion gas for the burner 18.
  • the air mixing layer 46 is filled with ceramic balls each having a predetermined diameter. When air passes through the air mixing layer 46, the ceramic balls bend the flow path to efficiently mix the gases.
  • the air inlets 43 are formed in the lower portion of the air mixing layer 46, i.e., near the end portion on the upstream side of the air mixing layer 46.
  • the diameter of each ceramic ball is set to 1/3 to 1/10 the width of the flow path in the air mixing layer 46 in consideration of an increase in flow resistance and mixing efficiency. If the diameter of each ceramic ball is 1/3 or more the width of the flow path, mixing cannot be sufficiently done. If this diameter is 1/10 or less, the flow resistance undesirably increases.
  • This flow path is connected to the supply port 26 for a fluid mixture of a reformation material gas and steam at the upper portion. Since the third intermediate cylinder 63 is attached to an upper portion with a space being ensured at a lower portion, the cooling fluid path 48 is divided in the radial direction at the third intermediate cylinder 63 as a boundary.
  • the outer path portion serves as a descending path contacting the PROX layer 12, and the inner path serves as an ascending path contacting the shift layer 11.
  • the main cooling fluid flowing through the cooling fluid path 48 is a fluid mixture of a reformation material gas and reforming water. As will be described later, another fluid may pass through this flow path.
  • the shift layer (CO converter catalyst layer) 11 is formed between the fourth and fifth intermediate cylinders 64 and 65.
  • the shift layer 11 is filled with a CO converter catalyst.
  • the shift layer 11 is connected to a heat recovery layer 50 at an upper portion and connected to the PROX layer 12 at a lower portion and perform a CO transforming reaction.
  • the fifth intermediate cylinder 65 is connected to the bottom portion of the first intermediate cylinder 61 at a lower portion.
  • the fifth intermediate cylinder 65 serves as the inner wall of the shift layer 11, and the sixth intermediate cylinder 66 serves as the outer wall of the heat recovery layer 50.
  • a space is defined between these walls and serves as a heat insulating layer 49 for insulating heat between these walls and also serves as a buffer mechanism for buffering a thermal stress between the walls.
  • the heat recovery layer 50 filled with ceramic balls is formed between the sixth and seventh intermediate cylinders 66 and 67.
  • the diameter of each ceramic ball is 1/2 to 1/5 the width of the path in the heat recovery layer 50. If the diameter of each ceramic ball exceeds 1/2 the width of the path, the heat transfer efficiency decreases. If this diameter is 1/5 or less the width of the path, the flow resistance undesirably increases.
  • the ceramic balls have the function of transferring the heat of a gas passing through the heat recovery layer 50 to the reforming catalyst layer 13 contacting the heat recovery layer 50 via the seventh intermediate cylinder 67.
  • a bottom plate 76 is attached to the lower portion of the sixth intermediate cylinder 66.
  • a space is defined between the bottom plate 76 and a bottom plate 78 attached to the lower portion of the inner cylinder 68.
  • a preheat layer 51 is disposed in the annular space defined between the seventh intermediate cylinder 67 and the inner cylinder 68 on the upstream side.
  • This preheat layer 51 is also filled with a filler for improving the heat transfer effect, e.g., ceramic balls each having a diameter of 1/2 to 1/5 the width of the path.
  • the reforming catalyst layer 13 is formed on the downstream side of the preheat layer 51.
  • the preheat layer 51 communicates with the cooling fluid path 48 on the upstream side.
  • the reforming catalyst layer 13 is filled with a reforming catalyst for performing steam reforming for a reformation material gas.
  • the reforming catalyst layer 13 communicates, at its lower portion, with the lower end of the heat recovery layer 50 via the space defined between the bottom plate 78 of the inner cylinder 68 and the bottom plate 76 of the sixth intermediate cylinder 66.
  • the space between the bottom plate 78 and the bottom plate 76 also serves as a heat insulating layer for a portion burnt by the burner 18.
  • the cylindrical heat transfer partition wall 14 is located inside the inner cylinder 68 at a proper distance from the bottom plate 78.
  • the space between the heat transfer partition wall 14 and the inner cylinder 68 serves as an exhaust gas path through which the exhaust gas burnt by the burner 18 flows, and is connected to the combustion exhaust gas outlet 24 at an upper portion.
  • a steam generator 34 is located inside the upper portion of the heat transfer partition wall 14.
  • the steam generator 34 is a gap having the heat transfer partition wall 14 as one surface.
  • a partition wall 35 is disposed in the gap to partition it into inner and outer portions, which respectively communicate with the steam outlet 20 and water supply port 22.
  • the wet steam outlet 21 is attached to the side of the steam generator 34 which opposes the outlet of the water supply port 22.
  • the steam outlet 20 and wet steam outlet 21 are connected to the supply port 26 for a fluid mixture of a reformation material gas and steam via regulating valves B (see Fig. 4) for regulating flow rates.
  • the burner 18 is located in the center of the heat transfer partition wall 14.
  • the burner 18 is disposed at a position where the nozzle is located below the lower end of the steam generator 34. Therefore, when the burner 18 is turned on and a flame comes from the nozzle, the flame does not directly touch the steam generator 34.
  • Fig. 4 is a horizontal sectional view taken along a line IV - IV in Fig. 3. Note that an illustration of the supply ports and outlets which are unnecessary for the following description is omitted.
  • Reforming water a is supplied to the steam generator 34 of the reformer 81 via a water supply valve A and the water supply port 22. At start-up, it takes a predetermined time to extract saturated or superheated steam b1 from the steam generator 34 via the superheated steam outlet 20 by turning on the burner 18 and performing heating operation using the burner 18. As the heating process by the burner 18 progresses and the temperature in the reformer rises, a predetermined amount of saturated or superheated steam b1 is extracted from the superheated steam outlet 20.
  • a reformation material gas c to be reformed is supplied via a reformation material gas supply regulating valve C.
  • the reformation material gas c is fed into the reformer via the fluid supply port 26, together with the superheated steam b1 with which the reformation material gas c merges. Steam reforming for the reformation material gas c is then started in the reformer.
  • the supply of the saturated or superheated steam b1 is stopped to shift the operation of the reformer from the start-up operation state to the steady operation state.
  • the regulating valve B is operated to supply wet steam b2 containing liquefied water which is discharged from the wet steam outlet 21 communicating with the steam generator 34.
  • the water supply valve A is opened to supply the water a from the water supply port 22 to the steam generator 34 in the reformer (F-1).
  • the burner 18 mounted in the reformer is turned on to start the reformer (F-2).
  • the reformation material gas c to be reformed with which the superheated steam b1 is mixed, is fed into the reformer.
  • the temperature in the reformer is gradually raised by combustion performed by the burner 18.
  • a temperature T at an inflection point P of the shift layer 11 is detected as a reference value for a shift to the steady operation (F-3). It is checked whether the inflection point temperature T is 200°C or more (F-4).
  • the regulating valve B is gradually opened (F-5) to supply the wet steam b2 containing liquefied water, while mixing it with the reformation material gas c, in place of the superheated steam b1.
  • the temperature in the reformer lowers. It is checked whether the return temperature T falls within the range from 170°C and 230°C both inclusive (170°C ⁇ T ⁇ 230°C) (F-6).
  • the opening degree of the regulating valve B is regulated to suppress an increase in the amount of wet steam b2 supplied.
  • the opening degree of the regulating valve B is regulated to increase the amount of wet steam supplied (F-7).
  • the reforming water a is supplied from the water supply port 22 into the steam generator 34.
  • the burner 18 is then turned on to heat the inside of the reformer 81.
  • the heat transfer partition wall 14 is heated by radiation heat from the flame.
  • the combustion exhaust gas passes between the heat transfer partition wall 14 and the inner cylinder 68 and is discharged from the combustion exhaust gas outlet 24, thereby internally heating the reforming catalyst 13 and preheat layer 51.
  • the steam generator 34 is gradually heated by the combustion exhaust gas passing between the heat transfer partition wall 14 and the inner cylinder 68, a rise in temperature in the combustion chamber of the burner 18, and transfer of heat from the heat transfer partition wall 14.
  • the steam b1 is extracted from the steam outlet 20.
  • the steam b1 is then supplied through the reformation material gas supply port 26 after the reformation material gas c is added to the steam.
  • the steam generator 34 Since the steam generator 34 is heated by the combustion performed by the burner 18 in this manner, the steam b1 required to start the reformer 81 can be obtained in a relatively short period of time.
  • the combustion exhaust gas from the burner 18 pass between the heat transfer partition wall 14 and the inner cylinder 68, the heat in the combustion exhaust gas is absorbed and effectively used, thus improving the efficiency.
  • the reformation material gas c is a hydrocarbon-based fuel such as town gas.
  • This gas passes through the cooling fluid path 48 formed between the second and fourth intermediate cylinders 62 and 64 and is set to the preheat layer 51.
  • the steam b1 and reformation material gas c supply heat to the shift layer 11 and PROX layer 12.
  • the steam b1 in particular, liquefies to supply latent heat, thus quickening rises in the temperatures of the shift layer 11 and PROX layer 12.
  • the reformation material gas c When the reformation material gas c enters the preheat layer 51, since the ceramic balls charged in the preheat layer 51 are heated by heat from the burner 18, the reformation material gas c absorbs the heat to be heated to a predetermined temperature, required for a reforming reaction, or higher. This gas then enters the reforming catalyst layer 13. Since the reformation material gas c and steam b1 which have low temperatures are supplied to the preheat layer 51, the temperature of the preheat layer 51 near the inlet can be suppressed low. If the reformation material gas c is methane gas, the reformation material gas c entering the reforming catalyst layer 13 is reformed by the following reaction: CH 4 + H 2 O ⁇ CO + 3H 2
  • the reaction proceeds while the combustion heat from the burner 18 is absorbed. More specifically, when the combustion exhaust gas from the burner 18 passes between the heat transfer partition wall 14 and the reforming catalyst layer 13, the heat of the combustion exhaust gas is absorbed by the reforming catalyst layer 13. In the reforming catalyst layer 13, a reforming reaction proceeds accompanying a rise in temperature. When the reaction reaches almost equilibrium, the reformed gas flows out of the lower portion of the reforming catalyst layer 13, reverses at the lower end, and enters the heat recovery layer 50.
  • the heat recovery layer 50 is filled with ceramic balls, and the heat of the reformed gas is supplied to the reforming catalyst layer 13 via the ceramic balls.
  • the upper end of the heat recovery layer 50 is in contact with the preheat layer 51 into which the reformation material gas c and steam b1 which have relatively low temperatures flow. For this reason, the temperature of the gas further lowers, and the gas flows out of the upper portion, with its temperature being set to a temperature suitable for a CO transforming reaction, reverses, and enters the shift layer 11.
  • the CO transforming reaction in the shift layer 11 is an exothermic reaction, since the shift layer 11 and heat recovery layer 50 are formed through a gap, the heat in the heat recovery layer 50 is not directly transferred to the shift layer 11 to heat it. This also makes it possible to suppress the temperature of the shift layer 11 low.
  • the reformed gas flowing out of the lower portion of the shift layer 11 reverses at the lower end and enters the PROX layer 12.
  • the PROX layer 12 is comprised of the PROX catalyst layer 44 and air mixing layer 46.
  • the reformed gas is mixed with the air fed from the air inlet 43 while passing through the air mixing layer 46, and a CO selective oxidizing reaction is performed by the PROX catalyst layer 44.
  • the air for CO selective oxidizing reaction transforms CO into CO 2 but oxidizes H 2 as well to consume H 2 .
  • the air mixing layer 46 is disposed on the front stage to supply a minimum necessary amount of oxygen to the reformed gas to selectively cause an oxidizing reaction for CO. In addition, such a reaction is caused in a plurality of stages.
  • the cooling fluid path 48 is formed between the shift layer 11 and the PROX layer 12, the time taken to obtain a temperature necessary for a reaction is shortened by heat from the steam b1 at start-up.
  • the regulating valve communicating with the wet steam outlet 21 is gradually opened to supply the wet steam b2 containing liquefied water from the reformation material gas supply port 26, together with the reformation material gas c.
  • the liquefied water contained in the wet steam b2 then absorbs the reaction heat in the shift layer 11 and PROX layer 12 to evaporate.
  • Rises in the temperatures of the shift layer 11 and PROX layer 12 due to an exothermic reaction are suppressed by an endothermic effect produced by this vaporization of moisture.
  • the temperature in the reformer can be maintained at a predetermined temperature.
  • the reforming water is heated by the heat of the shift layer 11 and PROX layer 12 to vaporize, the fuel that is heated by the steam generator 34 to generate steam can be saved.
  • the reformation material gas c is fed into the reforming catalyst layer 13 via the preheat layer 51, together with the heated steam.
  • the inside of the preheat layer 51 has already been heated by the burner 18, and the reformation material gas c and steam are heated by the preheat layer 51. For this reason, there is no need to separately prepare a preheat unit for raising the temperature of the reformation material gas c to the temperature required for the reforming catalyst layer 13, and the thermal efficiency can be improved. Furthermore, since the reformation material gas c is not supplied after it is heated to a high temperature, the temperature near the inlet of the preheat layer 51, e.g., the temperature at the outlet of the heat recovery layer 50, can be lowered. This makes it possible to continuously connect the shift layer 11, in which a reaction takes place at a temperature lower than the reaction temperature in the reforming catalyst layer 13, to the reforming catalyst layer 13 via the heat recovery layer 50.
  • the reformation material gas c heated by the preheat layer 51 is further heated by the reforming catalyst layer 13 to cause a reforming reaction.
  • the resultant gas then flows out of the lower portion of the reforming catalyst layer 13.
  • the reformed gas with a relatively high temperature which has flowed out of the lower portion of the reforming catalyst layer 13 ascends inside the heat recovery layer 50 and exchanges heat with the reforming catalyst layer 13 owing to the heat transfer promoting effect of the ceramic balls in the heat recovery layer 50.
  • the temperature of the gas lowers. That is, the heat recovery layer 50 has a temperature gradient exhibiting a decrease in temperature toward the upper portion of the heat recovery layer 50, and the heat of the reformed gas is absorbed and its temperature lowers as the gas ascends inside the heat recovery layer 50.
  • the same phenomenon occurs between the heat recovery layer 50 and the preheat layer 51.
  • the heat which the heat recovery layer 50 absorbs from the reformed gas is transferred from the heat recovery layer 50 to the preheat layer 51 by using the temperature difference.
  • the preheat layer 51 is formed before the reforming catalyst layer 13, and the inlet of the preheat layer 51 is located close to the outlet of the heat recovery layer 50.
  • CO contained in the reformed gas is transformed into carbon dioxide.
  • this reaction is an exothermic reaction, the temperature of the gas lowers to a temperature suitable for a CO selection oxidizing reaction upon heat exchange with the cooling fluid path 48, and the gas enters the next PROX layer 12.
  • the reformed gas contains about 0.5% of CO.
  • the heat insulating layer 49 is formed between the heat recovery layer 50 and the shift layer 11, the heat of the heat recovery layer 50 is insulated by the heat insulating layer 49, and the temperature of the shift layer 11 can be maintained at a predetermined temperature. In addition, any thermal stress due to the temperature difference between these layers can be eliminated to prevent damage.
  • the wet steam b2 is evaporated by the cooling fluid path 48 formed around the shift layer 11. This amounts to integrally incorporating a boiler portion in the layer.
  • the combustion heat generated by the burner 18 can be reduced, and the shift layer 11 and PROX layer 12 can be cooled by heat of evaporation to control the temperatures of the shift layer 11 and PROX layer 12 to a predetermined temperature.
  • the CO conversion ratio can be increased.
  • the PROX layer 12 a methanation reaction and reverse shift reaction, which are undesirable side reactions, can be suppressed.
  • the reaction heat and sensible heat in the shift layer 11 and PROX layer 12 can be recovered in this manner, the thermal efficiency can be improved.
  • combustion air gaseous or liquefied reforming water, a reformation material gas, or the like or a combination thereof may be used.
  • the cooling fluid path 48 is exclusively used for combustion air or the cooling fluid path 48 may be separated into paths to allow combustion air to flow therethrough. Reforming water, reformation material gas, or the like is fed into the reformer 81 by forming a path independently of these paths.
  • a sufficient cooling ability can be obtained, and the temperature can be arbitrarily lowered.
  • the reformed gas flowing out of the shift layer 11 enters the air mixing layer 46 in which it is mixed with air from the air supply port 30. Since the reformed gas is mixed with the air while passing through the air mixing layer 46, the gas is sufficiently agitated without using any agitating unit or the like. Since the reformed gas enters the PROX catalyst layer 44 in an agitated state, an unnecessary hydrogen loss due to local generation of high-concentration of oxygen by a reaction in the PROX catalyst layer 44 can be prevented. In addition, since a hole 43 can be arbitrarily set, air can be introduced from an arbitrary position in the PROX layer 12. This makes it possible to reduce the amount of air required for selective oxidization removal of CO and suppress a hydrogen loss due to excess air.
  • the gas enters the next PROX layer 12 to reduce the CO concentration again.
  • the reformed gas is extracted as a gas containing, for example, 75% of hydrogen, 5% of methane, 19% of carbon dioxide, 1% of nitrogen, and 10 ppm or less of carbon monoxide, from the reformed gas outlet 28.
  • the carbon monoxide concentration of the reformed gas is 10 ppm or less, the gas can be supplied to a polymer electrolyte fuel cell and used as a fuel gas for the polymer electrolyte fuel cell.
  • the amount of hydrogen generated is changed by adjusting the amount of reformation material gas supplied from the supply port 26.
  • the temperature at each portion must be kept almost constant in order to maintain a reaction. If, for example, the amount of reformed gas required decreases, and the amount of reformation material gas fed is decreased, the amount of reforming water must also be decreased. For this reason, the temperature of the shift layer 11 or PROX layer 12 may rise because of a reduction in the amount of cooling water.
  • the regulating valve communicating with the wet steam outlet 21 in the steam generator 34 is opened to decrease the amount of saturated or superheated steam fed from the superheated steam outlet 20.
  • the moisture of steam flowing from the supply port 26 increases, and hence the quantity of heat absorbed by latent heat increases. This prevents rises in the temperatures of the shift layer 11 and PROX layer 12 and unnecessary heat loss.
  • the temperature at each portion can be maintained without replenishing heat from another portion.
  • the steam generator 34 Since the steam generator 34 is heated by the transfer of heat through the heat transfer partition wall 14 and is not directly heated by the burner 18, even if the amount of reforming water to the steam generator 34 is decreased and the inside of the steam generator 34 is dried, the steam generator 34 is not overheated.
  • the regulating valves B communicating with the wet steam outlet 21 is closed to increase the amount of saturated or superheated steam b1 from the saturated or superheated steam outlet 20.
  • the temperatures of the shift layer 11 and PROX layer 12 can be maintained at a predetermined temperature without causing any unnecessary thermal loss.
  • temperature control is performed by using reforming water, good controllability can be obtained as compared with a case wherein combustion air or the like is used.
  • Fig. 6 shows another example of the compact, lightweight, single-pipe cylinder type reformer of the present invention as the third embodiment of the present invention.
  • a reformer 82 in a reformer 82, the inner bottom of an inner cylinder 65 is open, and the space between the inner cylinder 65 and an inner cylinder 66 is closed at an upper portion.
  • the other arrangements are the same as those of the reformer 81 shown in Fig. 3.
  • an air path 42 for supplying oxygen to a PROX layer 12 communicates with the space between a heat recovery layer 50 and a shift layer 11 to improve the heat insulating effect for the shift layer 11.
  • the bottom portion of the heat recovery layer 50 is not located close to the bottom portion of the shift layer 11, heat radiation from the bottom portion of the reformer 82 can be suppressed.
  • the PROX layer 12 is separated into the PROX layers 12a and 12b to form two layers on the outermost layer of the reformer 82.
  • the PROX layer 12 may be a single layer or constituted by three or more layers.
  • the shift layer 11 may also be formed on the outermost layer to form two layers, i.e., the shift layer 11 and PROX layer 12, on the outermost layer.
  • a CO remover as the PROX layer 12 may be provided independently of the reformer 82, and the outermost layer of the reformer 82 may be formed by only the shift layer 11.
  • Fig. 7 shows still another example of the compact, lightweight, single-pipe cylinder type reformer of the present invention as the fourth embodiment of the present invention.
  • a sub-shift layer 27 is formed on an upper portion (downstream side) of a heat recovery layer 50.
  • a second shift layer 11b is also formed in an annular flow path on the outermost layer, and the shift layer 11b and a PROX layer 12 are separately formed on the outermost layer.
  • the length of the annular flow path defined by a shift layer 11a and the PROX layer 12 and/or the second shift layer 11b in the axial direction is smaller than that of the heat recovery layer 50, and the lower end portions of these layers do not reach a portion near the bottom portion of an outer cylinder 10.
  • the space between the outer cylinder 10 and a bottom plate 76, the space between the bottom plate 76 and a bottom plate 78, the space around the heat recovery layer 50, i.e., the space between a sixth inner cylinder 66 and the outer cylinder 10, and the space between the heat recovery layer 50 and a shift layer 11, i.e., the space between the sixth inner cylinder 66 and a fifth inner cylinder 65, are filled with a heat insulator 53.
  • a partition plate 17 is disposed in an annular flow path in the outermost layer formed between first and second inner cylinders 61 and 62, i.e., between the second shift layer 11b and the PROX layer 12, so the shift layer 11b and the PROX layer 12 are separated from each other by the partition plate 17.
  • Eight outlets 23 are formed in the downstream outer wall of the shift layer 11b at almost equal intervals in the circumferential direction.
  • One inlet 25 is formed in the upstream outer wall of the PROX layer 12 to oppose the position of a supply port 30 for PROX air.
  • the space between the outer cylinder 10 and the bottom plate 76 and the space between the bottom plate 76 and the bottom plate 78 are filled with the heat insulator, dissipation of heat from a portion near the bottom portion can be prevented to prevent an unnecessary heat loss from the reformer 83. This improves the thermal efficiency.
  • the space between the circumferential portion of the heat recovery layer 50 and the outer cylinder 10 and the space between the heat recovery layer 50 and the shift layer 11 are filled with the heat insulator, the transfer of heat from the heat recovery layer 50 can be prevented, and a heat loss in the heat recovery layer 50 can be reduced. This can also suppress a rise in the temperature of the shift layer 11 and maintain its temperature at a predetermined temperature.
  • the formation of the heat insulator 53 near the bottom portion is not limited to the above example and may be applied to the reformer 81 or 82 shown in Fig. 3 or 6.
  • the annular flow path defined by the shift layer 11a, second shift layer 11b, and the PROX layer 12 is shortened in the axial direction, the amount of heat transferred from the heat recovery layer 50 to the shift layer 11a and second shift layer 11b can be reduced, and the temperature of the shift layer which is likely to be overheated by the heat from the heat recovery layer 50 can be maintained at a proper temperature, thus preventing a decrease in CO conversion ratio in the shift layer.
  • the sub-shift layer 27 is formed on the upper portion of the heat recovery layer 50, i.e., the downstream side, a rise in the temperature of the sub-shift layer 27 can be quickened. Since the catalyst effect of the sub-shift layer 27 is quickly activated immediately after start-up operation, the starting time required for the reformer 83 can be shortened. A length for the sub-shift layer 27 is properly selected in accordance with a reduction in starting time by the formation of the sub-shift layer 27, the degree of overheating of the sub-shift layer 27 in a steady operation period, and the like.
  • the sub-shift layer 27 is continuously formed on the upstream side of the shift layer 11a.
  • a single-pipe cylinder type reformer may be formed by using only the sub-shift layer 27, and a catalyst unit or the like having main shift layers and the like may be independently connected to the single-pipe cylinder type reformer.
  • a rise in the temperature of the sub-shift layer 27 in the single-pipe cylinder type reformer is quickened, and a catalyst reaction in the sub-shift layer 27 can be caused at an early stage, thus shortening the starting time and the like.
  • the eight outlets 23 are formed in the downstream outer wall of the second shift layer 11b at almost equal intervals in the circumferential direction, and one inlet 25 is formed in the upstream outer wall of the PROX layer 12 to oppose the supply port 30 for PROX air.
  • a reformed gas passing through the second shift layer is discharged from the video signal processing/switching circuit 23 and merges with the air supplied from the air supply port 30 in a space 31.
  • the reformed gas merging with the air is fed into the PROX layer 12 via the inlet 25.
  • the reformed gas passing through the shift layer 11 reliably merges with air, and only one inlet 25 is formed, the reformed gas and the air are sufficiently mixed when they are fed from the inlet 25. Since the reformed gas is fed into the PROX layer 12 after the gas and air are sufficiently agitated, a selective oxidizing reaction is efficiently performed. As a consequence, the amount of hydrogen consumed in the selective oxidizing reaction can be minimized to reduce the CO concentration to a predetermined value or less.
  • the second shift layer 11b is formed on the lower portion of the PROX layer 12.
  • the second shift layer 11b need not be formed on the lower portion of the PROX layer 12.
  • a reformed gas passing through the shift layer 11a is discharged into the space 31 and agitated together with air. The gas is then fed into the PROX layer 12.
  • the overall structure may be formed by the second shift layer 11 without forming the PROX layer 12. In this case, a unit or the like having a CO selective oxidizing function is connected to the above structure, as needed.
  • the heat insulator need not always be charged into all the portions described above. Charging of a heat insulator may be properly omitted in accordance with various conditions, e.g., the length of each portion of the reformer 83, operating temperature, and the intervals between the respective portions.
  • the eight outlets 23 are formed at almost equal intervals in the circumferential direction, and one inlet 25 is formed.
  • the present invention is not limited to this, and inlets may be formed at a plurality of positions.

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EP00917380A 1999-04-20 2000-04-20 Zylindrischer einrohr-reformer und verfahren zu dessen verwendung Withdrawn EP1094031A4 (de)

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JP11226799 1999-04-20
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PCT/JP2000/002581 WO2000063114A1 (fr) 1999-04-20 2000-04-20 Reformeur cylindrique monotube et procede pour faire fonctionner ledit reformeur

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US20010029735A1 (en) 2001-10-18
WO2000063114A1 (fr) 2000-10-26
US6481207B2 (en) 2002-11-19
CA2335483C (en) 2005-03-29
EP1094031A4 (de) 2005-02-02
AU774857B2 (en) 2004-07-08
JP3625770B2 (ja) 2005-03-02
CA2335483A1 (en) 2000-10-26

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